EP3649076B1 - A method for inter-bed cooling in wet gas sulfuric acid plants - Google Patents

A method for inter-bed cooling in wet gas sulfuric acid plants Download PDF

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EP3649076B1
EP3649076B1 EP18734213.4A EP18734213A EP3649076B1 EP 3649076 B1 EP3649076 B1 EP 3649076B1 EP 18734213 A EP18734213 A EP 18734213A EP 3649076 B1 EP3649076 B1 EP 3649076B1
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process gas
bed
steam
inter
sulfuric acid
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French (fr)
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EP3649076A1 (en
EP3649076C0 (en
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Mads Lykke
Martin MØLLERHØJ
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Topsoe AS
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Haldor Topsoe AS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/77—Fluidised-bed processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00—Methods of steam generation characterised by form of heating method
    • F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/765—Multi-stage SO3-conversion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/775—Liquid phase contacting processes or wet catalysis processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/80—Apparatus
    • C01B17/803—Converters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/80—Apparatus
    • C01B17/806—Absorbers; Heat exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194—Tubes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a method for inter-bed cooling of process gas between catalytic layers or beds in a wet gas sulfuric acid (WSA) plant, in which sulfuric acid is produced from acid feed gases containing sulfurous components like SO 2 , H 2 S, CS 2 and COS or liquid feeds like molten sulfur or spent sulfuric acid originating from alkylation technologies or so-called BTX production.
  • WSA wet gas sulfuric acid
  • Sulfuric acid (H 2 SO 4 ) is an important commodity chemical, the production of which exceeds 200 million t/year. It is primarily used for fertilizer production, but it is also used i.a. in the manufacture of viscose fibers, pigments, in batteries, in the metallurgical industry and in refining industry.
  • the sulfurous feed components are typically converted into SO 2 in a thermal combustor.
  • an industrial SO 2 converter is normally configured as a number of adiabatic catalytic beds with inter-bed cooling to increase the total conversion.
  • the SO 3 formed is reacted with H 2 O to form H 2 SO 4 , and then the H 2 SO 4 is separated from the gas phase in a condensation step, producing concentrated commercial grade H 2 SO 4 and a cleaned process gas, either to be sent directly to a stack or to be sent to further cleaning before being emitted to the atmosphere.
  • a high degree of energy recovery either reduces the need for any (expensive) support fuel/heat or increases the export of high value energy, e.g. as high pressure steam.
  • the normal configuration of the heat exchanger system for a WSA plant includes steam superheaters for the inter-bed cooling.
  • the saturated steam is produced in the waste heat boiler and the process gas cooler.
  • the steam produced in the waste heat boiler is insufficient for the inter-bed cooler(s), and therefore a steam cooler (de-superheating of steam by boiling water or pre-heating boiler feed water) is necessary.
  • the result is a complicated and expensive heat exchanger layout.
  • a WSA plant In a WSA plant, there is water and SO 3 vapor present in the converted process gas, and thus liquid sulfuric acid will condense if the temperature is below the sulfuric acid dew point.
  • the process gas temperature at the inlet of the sulfuric acid condensation step is typically limited to maximum 290°C due to the use of fluorinated polymers in the inlet of the WSA condenser.
  • a WSA plant can typically be designed for a sulfuric acid dew point up to 260-263°C at the inlet of the WSA condenser.
  • the saturated steam temperature in the steam system is typically selected to be 12-15°C higher than the sulfuric acid dew point, i.e. 275°C which gives 15°C temperature approach in the cold end of the process gas cooler.
  • a saturated steam temperature of 275°C is equivalent to a steam pressure of 58.5 barg.
  • US 2015/0352510 A1 discloses an adiabatic multi-bed catalytic converter with inter-bed cooling.
  • This converter comprises a pressure vessel, a plurality of super-imposed catalytic beds, each being configured with a cylindrical annular container and an axial core passage, and means for inter-bed cooling of a gas stream between at least two of said catalytic beds.
  • the means for inter-bed cooling includes a heat exchanger comprising heat exchange bodies, which extend axially through the core passages of at least two consecutive catalytic beds, and a wall system, which is also arranged in said core passages and surrounds said heat exchange bodies, to define a boundary of a shell side of the heat exchanger.
  • the wall system is structured in such a way that the shell side of the heat exchanger comprises at least a first space and a second space, and therefore the means for inter-bed cooling has nothing in common with a water tube boiler.
  • EP 2 610 001 A1 also describes an adiabatic multi-bed catalytic converter with inter-bed cooling as well as a related process.
  • This converter comprises a shell, which includes at least an inlet for a stream of fresh reagents and an outlet for a product stream, a number of catalytic beds arranged in series, and a number of inter-bed heat exchangers fed with a cooling medium and arranged to cool a process stream flowing from one bed to another.
  • the process related to the converter comprises a plurality of adiabatic reaction steps through respective catalytic beds arranged in series, so that a process stream exiting the first bed or an intermediate catalytic bed is fed to the next catalytic bed, and the process stream exiting the last catalytic bed forms the product stream.
  • the inter-bed cooling steps provide that a process stream is cooled by indirect heat exchange with a cooling medium.
  • the process is characterized in that at least one process stream, leaving a generic first catalytic bed for passage into a second and downstream catalytic bed, is mixed with a quench flow of reagents, allowing for a precise control of the temperature of the process stream, before entering the second bed, said quench flow having a temperature lower than the temperature of the process stream.
  • the inter-bed cooling may be obtained using a water tube boiler.
  • US 2015/0147266 A1 belonging to the Applicant, relates to a process plant for the oxidation of SO 2 to SO 3 , in which an oxidized process gas is cooled in an inter-bed cooler and subsequently subjected to further cooling by heat exchange in a boiler, which preferably is a water tube boiler.
  • a boiler which preferably is a water tube boiler.
  • Said boiler is, however, not used for inter-bed cooling within the converter, but rather for subsequent cooling after the converter, and the type of inter-bed cooler used is not specified.
  • the present invention provides a process layout, where high sulfuric acid production, high heat recovery and low complexity are combined, providing optimal operation of the plant without the loss of operability and flexibility.
  • the investment cost of this new layout is lower than that of the currently used plant layout.
  • the idea of the invention is to use water tube boilers for inter-bed cooling as an alternative to superheaters. This will result in a significant simplification of the overall process layout and substantial cost reductions due to a lower total heat exchange area.
  • the reason for the reduced heat exchanger area is the higher temperature approach in a boiler compared to a superheater and a higher heat transfer coefficient of boiling water compared to steam.
  • the present invention relates to a method for the cooling of process gas between catalytic layers or beds in a wet gas sulfuric acid plant, in which sulfuric acid is produced from feed gases containing sulfurous components like SO 2 , H 2 S, CS 2 and COS or liquid feeds like molten sulfur or spent sulfuric acid, wherein one or more boilers are used instead of conventional steam superheaters to cool the process gas between the catalytic beds in the SO 2 converter of the plant.
  • the inter-bed boilers used according to the invention are preferably water tube boilers, especially horizontal or approximately horizontal water tube boilers. Fire tube boilers and vertical water tube boilers can also be used, but the horizontal water tube boiler is the most cost efficient embodiment.
  • the tubes in the water tube boilers can be bare, fitted with fins or have a combination of finned and bare tubes in the tube bank.
  • the process gas preferably originates from combustion of at least one feed stream of spent sulfuric acid.
  • At least one of the feed streams to the plant is a CS 2 and H 2 S containing gas from a viscose fiber production plant.
  • the inter-bed cooling will typically be carried out in a heat exchanger using molten heat transfer salt, process gas (converted or unconverted), air or steam (saturated or superheated) or by quenching with colder air or process gas.
  • process gas converted or unconverted
  • air or steam saturated or superheated
  • quenching with colder air or process gas for most plants, the inter-bed cooling of the process gas is carried out with high pressure steam, cooling the process gas by superheating the steam.
  • the process gas temperature is then controlled by adjusting the flow of steam to the inter-bed cooler, i.e. usually there is a steam bypass around the inter-bed cooler.
  • the inter-bed cooler can be placed within the SO 2 converter shell as well as on the outside of the converter shell.
  • inter-bed coolers located inside the SO 2 converter shell, such that the cold areas of the heat exchanger are avoided, thus reducing the risk of sulfuric acid condensation and corrosion.
  • a typical wet gas sulfuric acid (WSA) plant configured for the treatment of a CS 2 and H 2 S containing lean gas from a viscose fiber production plant and producing sulfuric acid, is shown in Fig. 1 .
  • the lean gas will be atmospheric air with CS 2 + H 2 S ⁇ 2 vol%.
  • the lean gas (1) is split into two parts, of which about 1/3 is sent to the thermal combustor (6) via line (3), where it is combusted together with fuel gas (7) which is needed to maintain a sufficiently high temperature in the combustor.
  • the required oxygen for the combustion is contained in the lean gas.
  • molten sulfur (8) can be fed to the combustor to boost the acid production and heat input to the combustor.
  • the remaining 2/3 of the lean gas (4) bypasses the combustor and is used to quench the combustor flue gas (11) which is then fed to the SO 2 converter (12).
  • the CS 2 and H 2 S contained in the bypassed lean gas is oxidized to SO 2 , CO 2 and H 2 O in a first adiabatic catalytic bed (13) active for complete oxidation of H 2 S and CS 2 .
  • the heat of oxidation of H 2 S and CS 2 will typically increase the process gas temperature by 80-150°C.
  • the SO 2 -containing process gas now enters the first adiabatic SO 2 oxidation bed (14) which is loaded with sulfuric acid catalyst active for oxidation of SO 2 to SO 3 .
  • the first SO 2 converter bed the majority of the SO 2 is oxidized to SO 3 , which increases the process gas temperature at which the highest possible SO 2 conversion is below the emission requirements and thus a cooling step and another conversion step is required.
  • the inter-bed cooler (15) the partially converted process gas is cooled to the optimum inlet temperature of the second SO 2 converter bed, where the final SO 2 conversion takes place, bringing the overall SO 2 conversion into the 98-99.5 % range.
  • the process gas is then cooled in the process gas cooler (17) before it is sent to the WSA condenser (19).
  • H 2 SO 4 is partially reacting with H 2 O to form gaseous H 2 SO 4 .
  • the process gas is cooled to about 100°C, the hydration of SO 3 to H 2 SO 4 is completed, and H 2 SO 4 is condensed to form liquid concentrated H 2 SO 4 which leaves the WSA condenser via line (40).
  • the clean gas leaves the WSA condenser via line (20).
  • the clean gas may be sent for additional SO 2 removal in e.g. a caustic or peroxide scrubber or an acid mist filter (not shown in Fig. 1 ) before hot air is added via line (37) and the gas is sent to stack via line (21).
  • the cooling medium for the WSA condenser is ambient air (31) compressed in the cooling air blower (33) and sent to the WSA condenser via line (34), leaving the WSA condenser via line (35).
  • Demineralized water (50) is sent to the de-aerator (51) where oxygen is stripped off using low pressure steam (52)
  • the deaerated boiler feed water leaves the deaerator via line (56) and the pressure is increased by the boiler feed water pump (57).
  • the boiler feed water (58) is then preheated in the boiler feed water preheater (59) before it goes to the steam drum (62) via line (61).
  • a small part of the boiler feed water is used for quenching the export steam (75).
  • the high pressure steam drum is connected to two boilers, namely the process gas cooler (17) and the steam generator (80). Saturated steam leaves the steam drum via line (72), and it is superheated in the inter-bed cooler (15).
  • the superheated steam is then sent to the steam generator (80) via line (73), where it is de-superheated, while saturated steam is produced in the steam generator.
  • a part of the de-superheated steam is sent to the boiler feed water (BFW) preheater (59) where the steam is condensed and the heat is used for preheating the boiler feed water.
  • the steam condensate leaves the BFW preheater via line (77) and is returned to the deaerator (51).
  • the remaining partially de-superheated steam (75) is throttled to the desired export steam pressure and quenched to near saturation using boiler feed water from line (63) and sent to battery limit as export steam via line (64).
  • the described highly efficient and integrated heat management system is necessary to provide sufficient saturated steam to the inter-bed cooler, such that the process gas can be cooled to the optimal inlet temperature to the second SO 2 conversion catalyst bed.
  • the heat exchangers are closely linked and have a rather narrow operating window in which the energy balance is in favor of producing sufficient or surplus amounts of saturated steam.
  • a wet gas sulfuric acid (WSA) plant using the present invention configured for treatment of a CS 2 and H 2 S containing lean gas from a viscose fiber production plant is shown in Fig. 2 .
  • the process gas layout of the present invention is largely similar to the traditional layout as described above.
  • the difference between the traditional layout of the WSA plant and the new layout according to the invention is within the thermal management of the plant.
  • demineralized water (50) is sent to the de-aerator (51) where oxygen is stripped off using low pressure steam (53).
  • the de-aerated boiler feed water leaves the de-aerator via line (56), and the pressure is increased by the boiler feed water pump (57).
  • the boiler feed water is sent further to the steam drum (62) via line (58).
  • the steam drum is connected to two boilers, namely the process gas cooler (17) and the inter-bed cooler (19) which, in this layout, is configured as a boiler and not as a steam superheater as in the traditional layout.
  • the saturated steam from the steam drum (83) can optionally be throttled before it is sent to battery limit as export steam via line (64).
  • the main task of the inter-bed cooler is to control the process gas temperature to the downstream catalytic bed and, with a boiler installed, the process gas temperature is controlled by leading a fraction of the hot process gas around the boiler via line (85).
  • the inter-bed cooler is a steam generator (boiler), which can be of the fire tube type as well as of the water tube type.
  • the fire tube boiler will typically have to be positioned outside the SO 2 converter shell, with an increased risk of creating cold spots and consequently condensation and corrosion by sulfuric acid. Due to the thick shell of a fire tube boiler, this boiler option is considered to be uneconomical.
  • a water tube boiler inside the SO 2 converter shell is the preferred solution because the tubes can be oriented in any position from horizontal to vertical, and moreover the tubes can be bare or finned.
  • 30,000 Nm 3 /h viscose off-gas containing 0.38 vol% CS 2 , 0.36 vol% H 2 S and ambient air as balance is treated in a WSA plant as shown in Figs. 1 and 2 , respectively.
  • 400 kg/h molten sulfur (7) is incinerated to boost the sulfuric acid production and to add supplemental heat for the thermal combustor, and 80 kg/h low pressure steam (54) is used for atomization of the molten sulfur.
  • Natural gas (8) is added to the thermal combustor to achieve a temperature of 850°C in the thermal combustor (6).
  • the resulting process gas contains 2-3 vol% SO 2 after the catalytic oxidation of CS 2 and H 2 S.
  • the sulfuric acid dew point temperature in the process gas stream (18) at the inlet of the WSA condenser (19) is 238°C only. Therefore, the inlet temperature to the WSA condenser and also the saturated steam temperature in the steam system has been reduced to 270°C and 255°C, compared to the maximum values of 290°C and 263°C, respectively.
  • This provides a minimum 17°C margin to the sulfuric acid dew point in the inter-bed cooler (15)/inter-bed boiler (19) and process gas cooler (17) and 15°C temperature approach in the cold end of the process gas cooler (17).
  • the steam pressure corresponding to a saturated steam temperature of 255°C is 42.2 barg.
  • the reason for reducing the steam pressure and the inlet temperature to the WSA condenser in this example is to maximize the steam production, and to reduce the cost of the steam system by providing a lower design pressure.
  • Table 1 below shows the difference in number of heat exchangers in the heat recovery system used to control the process temperatures in the plant.
  • the number of heat exchangers is reduced from four in the traditional layout to only two in the improved heat recovery system.
  • the heat exchange area in the inter-bed cooler is reduced from 43 m 2 in the traditional layout (case A) to 8.5 m 2 in the new layout (case B).
  • This reduction in heat exchange area is partly due to the improvement in the overall heat transfer coefficient, as boiling water with an almost infinite heat transfer coefficient replaces a lower convective heat transfer coefficient of the saturated/superheated steam.
  • the increased temperature differences in the boiler compared to the steam superheater reduces the required heat transfer area. Additionally, there will be a further cost saving, as the boiler typically is made of carbon steel, whereas the steam superheater is made of a more expensive alloyed steel.
  • the inter-bed boiler now operates independently of the operation of the plant, i.e. the performance of the heat exchanger is not dependent on sufficient production of saturated steam for cooling of the process gas.
  • a dedicated steam superheater can be included and installed anywhere between the combustor outlet and the outlet of the final SO 2 catalyst bed.
  • a WSA plant is configured for regeneration of 100 MTPD spent sulfuric acid (101) containing about 90 wt% H 2 SO 4 , 4 wt% H 2 O, 0.3 wt% SO 2 and 5.7 wt% sulfur containing hydrocarbons.
  • the spent acid (101) is atomized into the thermal combustor (6) by using atomizing air (102), and the heat input required to maintain a combustor temperature of ⁇ 1000°C is supplied by burning fuel gas. Hot combustion air is supplied via line (141).
  • the thermal combustor (6) the spent acid is decomposed to SO 2 , H 2 O and CO 2 .
  • the process gas (116) from the combustor is sent to the waste heat boiler (110), where the process gas is cooled. In a further cooling step, the process gas is cooled in the air preheater (111). The process gas then enters the electrostatic precipitator (112) where the dust, mainly coming from corrosion products from the upstream alkylation process, is removed.
  • an SCR reactor (113) will be installed and a small amount of ammonia will then be added to the process gas via line (145).
  • preheated dilution air is added to the process gas via line (146).
  • the diluted process gas (122) then enters the SO 2 converter (12), which in this case is configured with three adiabatic catalytic beds (13, 14 and 124) containing a sulfuric acid catalyst active for the oxidation of SO 2 to SO 3 .
  • the majority of the SO 2 oxidation takes place, increasing the process gas temperature out of the catalyst bed to 500-550°C.
  • the first inter-bed cooler (19) the partially converted process gas is cooled before being sent to the second bed (14) for further conversion.
  • the further converted process gas is then sent to the second inter-bed cooler (123), where the process gas is cooled to the third bed (124) inlet temperature.
  • the final SO 2 conversion ensures an overall SO 2 conversion of about 99-99.7%.
  • the process gas is then cooled in the process gas cooler (17).
  • the converted process gas (18) is then sent to the WSA condenser (19) for further cooling to about 100°C, hydration of SO 3 to H 2 SO 4 and condensation of the H 2 SO 4 .
  • the cooling medium for the WSA condenser is ambient air which is compressed in the cooling air blower (33).
  • a fraction (138) of the hot air (35) from the WSA condenser is further compressed in the hot air blower (139) and used as combustion air (141) in the combustor (6) and as dilution air (142).
  • the remaining hot air can be used for boiler feed water preheating in (159) and/or addition to the clean gas from the WSA condenser, which may optionally have been subjected to additional cleaning in e.g. a caustic or hydrogen peroxide scrubber and/or a mist filter (not shown in Fig. 3 ) .
  • the process gas cooling taking place in the waste heat boiler (110), the first and the second inter-bed cooler (19 and 123) and the process gas cooler (17) are by means of steam boilers, preferably water tube boilers.
  • the first and the second inter-bed coolers are both to be configured with a hot process gas bypass (85, 185) and a downstream mixer (not shown) to ensure optimal and uniform inlet temperature for the downstream catalyst beds.
  • All boilers are connected to the steam drum (62) via risers and downcomers (70/71, 81/82, 114/115 and 181/182). Finally, saturated export steam is withdrawn from the steam drum via line (64).
  • one of the two inter-bed coolers may be configured as a steam superheater similar to the layout shown in Fig. 1 .
  • the steam superheater can be placed anywhere between the outlet of the waste heat boiler (110) and the inlet to the SO 2 converter (12).
  • the sulfuric acid dew point temperature in the process gas stream (18) at the inlet to the WSA condenser (19) is 263°C due to a high content of both water and SO 3 vapor. Therefore, the inlet temperature to the WSA condenser and also the saturated steam temperature in the steam system is selected as the maximum values 290°C and 263°C, respectively. This provides a minimum 12°C margin to the sulfuric acid dew point in the inter-bed boilers (19, 123) and process gas cooler (17) and 15°C temperature approach in the cold end of the process gas cooler (17).
  • the inter-bed coolers are steam superheaters, using the saturated steam produced in the waste heat boiler (110) and the final process gas cooler (17).
  • the production of saturated steam is higher than in the case with the viscose off-gas (Example 1), the production is not high enough to ensure a simple control of the two inter-bed coolers.
  • the saturated steam is first passed through the second inter-bed cooler for first superheating and then to the first inter-bed cooler for final superheating, each cooler being equipped with a bypass system for control of the process gas temperature. Between the two inter-bed coolers it is necessary to add a steam de-superheater to allow for sufficient cooling of the process gas in the first interbed cooler.
  • the de-superheater is often a compact boiler, producing saturated steam for the steam cooling circuit.
  • the superheated steam leaving the first inter-bed cooler may also be required to pass through a de-superheater to produce more saturated steam for the steam cooling system.
  • the internal transfer of heat is only 5% of the total duty (see Table 1 in Example 1 for explanation), which again is reduced to 0% in the new layout of the invention.
  • the traditional steam cooling system has a very high heat recovery, but also interdependency between the heat exchangers. As the inter-bed coolers need saturated steam to function, the start-up of the plant can be long because the production of saturated steam must balance the need for cooling in the inter-bed coolers.
  • the new layout allows the same high heat recovery as the traditional layout with the use of fewer heat exchangers.
  • the inter-bed coolers will require less heat transfer area and the material of construction will be carbon steel as opposed to the higher alloyed steels employed for the traditional heat exchangers.
  • FIG. 4 A further example of the application of the present invention is shown in Fig. 4 .
  • a WSA plant is configured for treatment of an acid gas.
  • An acid gas containing 30 vol% H 2 S, 0.4 vol% CO, 0.1 vol% H 2 , 700 ppmv COS and CO 2 as balance is sent to the thermal combustor (6) via line (105).
  • the thermal combustor the acid gas is oxidized to SO 2 , CO 2 and H 2 O.
  • the required oxygen for the combustion and SO 2 oxidation is sent to the combustor as hot air via line (141).
  • the process gas from the combustor enters the waste heat boiler (110) via line (116). In the waste heat boiler, the process gas is cooled to the SO 2 converter inlet temperature.
  • the process gas may then be subjected to NO x reduction in the SCR reactor (113), and the required ammonia for the SCR reaction is added to the process gas via line (165).
  • the SO 2 containing process gas (122) then enters the SO 2 converter (12) which, like in Example 2, is configured with three adiabatic catalyst beds with interbed cooling carried out by the first and the second interbed cooler (19, 123).
  • the process gas cooler (17) the process gas is cooled to 290°C and the SO 3 is partially hydrated to H 2 SO 4 .
  • the converted process gas (18) is then sent to the WSA condenser for further cooling to about 100°C, hydration of SO 3 to H 2 SO 4 and condensation of concentrated H 2 SO 4 .
  • the cooling medium for the WSA condenser is ambient air which is compressed in the cooling air blower (33).
  • a fraction (138) of the hot air (35) from the WSA condenser is further compressed in hot air blower (139) and used as combustion air (141) in the combustor (6).
  • the remaining hot air can be used for boiler feed water preheating in (159) and/or addition to the clean gas from the WSA condenser, which may optionally have been subjected to additional cleaning in e.g. a caustic or hydrogen peroxide scrubber and/or a mist filter (not shown in Fig. 4 ).
  • the process gas cooling taking place in the waste heat boiler (110), the first and the second inter-bed cooler (19 and 123) and the process gas cooler (17) is achieved by means of steam boilers, preferably a fire tube boiler for the waste heat boiler and water tube boilers for the interbed cooler and process gas cooler.
  • the first and the second inter-bed coolers are both to be configured with a hot process gas bypass (85, 185) and a downstream mixer (not shown) to ensure an optimal and uniform inlet temperature to the downstream catalyst beds. All boilers are connected to the steam drum (62) via risers and downcomers (70/71, 81/82, 114/115 and 181/182).
  • one of the two inter-bed coolers may be configured as a steam superheater similar to the layout shown in Fig. 1 .
  • a dedicated steam superheater may be installed between the waste heat boiler (110) and the SO 2 converter (12) .
  • the sulfuric acid dew point temperature in the process gas stream (18) at the inlet to the WSA condenser (19) is 260°C due to a high content of both water and SO 3 vapor.
  • the inlet temperature to the WSA condenser and also the saturated steam temperature in the steam system are selected as 290°C and 260°C, respectively. This provides a minimum 15°C margin to the sulfuric acid dew point in the inter-bed boilers (19, 123) and process gas cooler (17) and 15°C temperature approach in the cold end of the process gas cooler (17).
  • the size and cost of the inter-bed coolers will still be significantly reduced, and the start-up of the plant with the new layout will still be faster.

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EP18734213.4A 2017-07-06 2018-06-26 A method for inter-bed cooling in wet gas sulfuric acid plants Active EP3649076B1 (en)

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CN112441565A (zh) * 2019-09-04 2021-03-05 中石化广州工程有限公司 一种硫磺回收claus尾气处理方法及装置
CN111249888B (zh) * 2020-03-03 2021-12-31 中国石油集团东北炼化工程有限公司 一种废硫酸湿法再生的尾气处理装置及工艺

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DE102010006541B4 (de) 2010-02-01 2016-03-17 Outotec Oyj Verfahren und Anlage zum Abkühlen von Säure
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CL2020000011A1 (es) 2020-07-24
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SA520410957B1 (ar) 2023-01-11
US11543120B2 (en) 2023-01-03
CA3068766A1 (en) 2019-01-10
EP3649076A1 (en) 2020-05-13
CN109205574A (zh) 2019-01-15
RU2020105255A3 (ar) 2021-10-19
RU2020105255A (ru) 2021-08-06
KR102614218B1 (ko) 2023-12-15
US20200149735A1 (en) 2020-05-14
PL3649076T3 (pl) 2023-11-06
BR112019028201A2 (pt) 2020-07-07
CN210393722U (zh) 2020-04-24
CA3068766C (en) 2024-03-12
RU2771445C2 (ru) 2022-05-04
EP3649076C0 (en) 2023-06-07

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